Copper-containing disazo dyestuffs



Patented such as pyridine, quinoline or others similar to these are 2,813,854 added to the alkaline solution.

The disazo dyestuffs can be converted into the copper COPPER'CONTAINING DISAZO DYESTUFFS complex compounds for example by heating the dyestulfs Ernst Iselin, Dornach, and Walter Wehrli, Riehen, Swit- 5 with pp salts in aqueous solution or suspension or in zerland, assignors, by mesne assignments, to Saul & a concentrated aqueous solution of an alkaline salt of 21 Co., Newark, N. J., as nominee of Fidelity Union Trust low-molecular aliphatic monocarboxylic acid, or by treatp y, executive trustee under 531N101 THIS! ing the dyestuffs with complex solutions of copper salts, e. g. copper tetrammine hydroxide, in an aqueous medium, No gfi fifif'gg figg 1956 if desired in the presence of aliphatic secondary or terziary bases such as diethanolamine or triethanolamine. Chums Priority, application Switzerland March 1955 The new cupriferous disazo dyestuffs dye cotton and 4 Claims. (CL 260 148) fibers of regenerated cellulose in bright blue shades of outstanding fastness to washing and light.

The following examples illustrate the invention without limiting its scope. All parts specified therein are by weight; all temperatures are in degrees centigrade.

The present invention relates to new valuable coppercontaining disazo dyestufls.

More particularly, the invention has especial relation to copper-containing disazo dyestuffs which, in their free Examplel acid form, correspond to the formula 24.4 parts of 4.4-diamino-3.3'-dimethoxy-1.1'-diphenyl o-c o 0 cuo N=N N=N nots- NH-C o-O HO;S SOIH SOIH wherein are tetrazotized in the normal way and combined in the presence of sodium carbonate at a temperature of 0$ with a solution of 46.7 parts of the sodium salt of 2-benzoylamino-S-hydroxynaphthalene 1.7 disulfonic acid in 500 parts of Water. When the formation of the intermediate compound is completed, it is fed while in solution with a further solution of 34.8 parts of the sodium salt of B038 SO33 u) 1-hydroxynaphthalene-3.fi-disulfonic acid and 400 parts of is the residue of 1-hydroxynaphthalene-3.6-disulfonic acid, water. The solution is stirred until the coupling reaction l-hydroxynaphthalene-3.S-disulfonic acid or l-hydroxy- 40 is completed; then the disazo dyestutf is isolated by an naphthalene-4.S-disulfonic acid. addition of sodium chloride to the coupling mass and The new copper-containing disazo dyestulfs are obtained filtered off. by coupling 1 mol of the tetrazo compound of 4.4-di For converting into the copper complex compound the amino-3.3'-dimethoxy-1.1-diphenyl in either order with moist filter-cake is added to a concentrated solution of 50 1 mol of the l-hydroxynaphthalene disulfonic acid correparts of crystallized copper sulfate, 100 parts of water and spending to formula (1) and 1 mol of 2-benzoylam'irro- 350 parts of crystallized sodium acetate at 80-90", the S-hydroxynaphthalene-1.7-disulfonic acid, and treating the solution is heated further and water distilled off in suffiresulting disazo dyestuff with a copper-yielding agent uncient quantity to allow to reach a temperature of 107. der conditions which allow the splitting of the methoxy The mass is then boiled for a further 12 hours on the regroups present in the dyestuff. flux. In order to isolate the dyestutf, it is drop-fed with Preferred l-hydroxynaphthalene disulfonic acids are, as water until the salts enter into solution, whilst the dyestufi indicated, 1-hydroxynaphthalene-3.G-disulfonic acid, l-hyremains undissolved. This is subsequently filtered ofi and droxynaphthalene-El.B-disulfonic acid and l-hydroxynaphdried. The copper-containing disazo dyestuff corresponds thalene-4.8-disulfonic acid. to the formula The coupling of the tetrazo compound with the aboveand is a dark powder which dissolves in water with a blue named azo components is carried out preferably in a soand in concentration sulfuric acid with a blue-green coloradium bicarbonate to sodium carbonate alkaline solution. tion, and dyes cotton and fibers of regenerated cellulose The second coupling reaction can be considerably accelcrin navy blue shades of outstanding fastness to light and ated and the yield increased when tertiary organic bases Washing.

3 Example 2 24.4 parts of 4.4'-diamino-3.3'-dimethoxy-1,1'-diphenyl are tetrazotized in the normal way and combined in the presence of sodium carbonate and at a temperature of -5 with a solution of 34.8 parts of sodium 1-hydroxynaphthalene-3.S-disulfonate and 500 parts of water. When the formation of the intermediate compound is completed, a solution of 46.7 parts of sodium 2-benzoylamino-5-hydroxynaphthalene-l.7-disulfonate in 600 parts of water is added to the mass. To accelerate coupling, 100 to 200 parts of a mixture of pyridine bases may be added to the reaction solution. The solution is stirred until the coupling is completed, and the disazo dyestuff thus obtained is isolated by filtering ofi.

For converting into the copper complex compound it is dissolved in 2000 parts of water, to which solution are added at a temperature of 80-90 parts of sodium carbonate and a solution of the copper tetrammine complex and is a dark powder which dissolves in water with a Example 3 100 parts of wetter-out cotton are entered at room temperature into a dyebath prepared with 3000 parts of water, 0.5 part of the concentrated dyestuff obtained according to Example 2, first and second paragraphs, and 10 parts of Glaubers salt. The dyebath is raised to the boil in the course of 30 minutes, during which time 10 parts of Glaubers salt are added at 40 and 10 parts at 80. The cotton is dyed for a further minutes at the boil. After this time a further 10 parts of Glaubers salt are added to the bath, which is then allowed to cool at 50 in the course of minutes. The cotton is removed from the dyebath, rinsed in running water, squeezed and dried. It is dyed in a bright blue shade of outstanding fastness to light and washing.

Having thus disclosed the invention what is claimed is:

1. A copper-containing disazo dyestufi' which, in its free acid form, corresponds to the formula wherein Hoes sUaH is a member selected from the group consisting of the l-hydroxynaphthalene-3.6-disulfonic acid, l-hydroxynaphblue coloration and in concentrated sulfuric acid with a thalene-3.8-disulonic acid and l-hydroxynaphthalene-4.8-

blue-green coloration, and dyes cotton and fibers of regenerated cellulose in bright blue shades of outstanding fastness to light and washing.

SOzH

34.8 parts of sodium l-hydroxynaphthalene-4.8-disulfonate can be employed with equal success in place of H038 O-Cu I N=N N= soil! 110.

34.8 parts of sodium l-hydroxynaphthalene-3.8-disulfonate. The thus-obtained copper-containing disazo dyestufi corresponds to the formula disulfonic acid residues.

2. The copper-containing disazo dyestufi which, in its free acid form, corresponds to the formula Cu-O SOaH

3. The copper-containing disazo dyestutf which, in its free acid form, corresponds to the formula 4. The copper-containing disazo dyestufi which, in its free acid form, corresponds to the formula BO;H 50111 References Cited in the file of this patent UNITED STATES PATENTS 1,889,732 Stusser et a1 Nov. 29, 1932 1,921,336 Wiedemann et a]. Aug. 8, 1933 2,620,331 Wehrli Dec. 2, 1952 

1. A COPPER-CONTAINING DISAZO DYESTUFF WHICH, IN ITS FREE ACID FORM, CORRESPONDS TO THE FORMULA 